茜素-聚乳酸/胶原蛋白纳米纤维膜的制备及其氨气检测性能

doi:10.13475/j.fzxb.20240506101

摘要/Abstract

摘要：

为探索开发一种用于氨气检测的比色纳米纤维材料,以茜素为检测探针,聚乳酸(PLA)、胶原蛋白(Col)为基材,利用静电纺丝技术制备了茜素-PLA/Col纳米纤维膜。借助紫外-可见分光光度计、扫描电子显微镜、差示扫描量热仪、X射线衍射仪和接触角测量仪等,对探针的颜色变化和纳米纤维膜的微观形貌和化学组成进行表征,并对纳米纤维膜的热稳定性、亲水性、可降解性、氨气检测性能以及可重复性进行了探究,并应用于鱼体新鲜度检测。结果表明:茜素溶液在pH值大于或等于7时具有敏感变色性能;随着氨气浓度增加,纳米纤维膜的颜色由黄色变为粉红色,再变为紫红色,最终变为紫色;纳米纤维膜具有良好的热稳定性、疏水性、可降解性及可重复检测性,其可用于鱼体新鲜度的比色检测。

关键词: 氨气检测, 静电纺丝, 茜素, 聚乳酸, 胶原蛋白, 检测探针, 纳米纤维膜

Abstract:

Objective Ammonia is a common toxic gas, widely existing in industrial, agriculture and living environment. Because of the strong corrosive and irritating nature of ammonia, it is a serious threat to human and animal life and health. Therefore, it is particularly important to develop a new type of testing material which is simple in operation, low in cost, and capable of achieving real-time non-destructive testing with visual characteristics.
Method An alizarin-PLA/Col nanofiber membrane was prepared by electrospinning using alizarin as probe and polylactic acid (PLA) and collagen (Col) as substrate. By means of UV-Vis spectrophotometer, scanning electron microscope, differential scanning calorimeter, X-ray diffractometer and contact angle measuring instrument, the color change of the probe and the micro-morphology and chemical composition of the nanofiber membrane were characterized, and the thermal stability, hydrophilicity, degradability, ammonia detection performance and repeatability of the nanofiber membrane were investigated.
Results Alizarin solution was adopted to produce different color changes under different pH conditions, and was used as a probe for ammonia detection. The addition of alizarin demonstrated no significant effect on the appearance of nanofibers, which have average diameter of about 190 nm, and are straight and evenly distributed in fineness. Infrared spectroscopy showed that compared with the PLA/Col nanofiber membrane, a new absorption peak appeared in the alizarin-PLA /Col nanofiber membrane at 896 cm^-1 because of the addition of alizarin, proving the successful dopping of alizarin into the nanofiber membrane. According to thermal performance analysis, the melting temperature of alizarin-PLA/Col nanofiber membrane was 341.2 ℃, indicating that the nanofiber membrane has good thermal stability in normal temperature environment. XRD analysis of alizarin-PLA/Col nanofiber membrane showed that the characteristic peaks of alizarin molecules did not appear in the alizarin-PLA/Col nanofiber membrane, indicating either that alizarin was uniformly dispersed in the nanofiber membrane or that alizarin was fully dissolved in the spinning solution, resulting in the disappearance of the original crystallization of alizarin. After addition of alizarin, the contact angle of the nanofiber membrane in water did not change obviously, suggesting that the addition of alizarin did not affect the hydrophilic and hydrophobic properties of the nanofiber membrane. With the increase of ammonia concentration, the color of the nanofiber membrane changes from yellow to red and finally to purple. Alizarin PLA/Col nanofiber membrane demonstrated a good performance of repeated detection of ammonia gas and reusability. In practical applications, the color of alizarin PLA/Col nanofiber membrane for the detection of fish body would visually change with time, and this meets the requirement of detecting the freshness of fish body. The addition of Col improved the hydrophilicity of the nanofiber membrane. The nanofiber membrane is self-degradable and hence environmentally friendly.
Conclusion Alizarin can be used as a probe for the detection of ammonia, which is easily combined with water and is weakly alkaline. The color of alizarin solution changed from light yellow to pink when the pH value was 6-7. With the increase of pH value, the color of alizarin solution gradually deepened, from pink to purple. With the increase of ammonia concentration, the color of the alizarin-PLA/Col nanofiber membrane can be changed from yellow to pink to purple, and the detection performance is good. Alizarin-PLA/Col nanofiber membrane has good biodegradability and will not pollute the environment after waste.In practical application, nanofiber membrane can also meet the freshness detection of fish.

Key words: ammonia detection, electrospinning, alizarin, polylactic acid, collagen, detection probe, nanofiber membrane

中图分类号:

TQ340.64

时晓聪, 陈莉, 杜迅. 茜素-聚乳酸/胶原蛋白纳米纤维膜的制备及其氨气检测性能[J]. 纺织学报, 2025, 46(05): 143-150.

SHI Xiaocong, CHEN Li, DU Xun. Preparation of alizarin-polylactic acid/collagen nanofiber membrane and its ammonia detection performance[J]. Journal of Textile Research, 2025, 46(05): 143-150.

导出引用管理器 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

链接本文: http://www.fzxb.org.cn/CN/10.13475/j.fzxb.20240506101

http://www.fzxb.org.cn/CN/Y2025/V46/I05/143

图/表 14

图1

图2

图3

图4

图5

图6

图7

图8

表1

图9

图10

图11

图12

图13

参考文献 22

[1]	ZHANG D, KANG Z, LIU X, et al. Highly sensitive ammonia sensor based on PSS doped ZIF-8-derived porous carbon/polyaniline hybrid film coated on quartz crystal microbalance[J]. Sensors and Actuators B: Chemical, 2022. DOI:10.1016/j.snb.2022.131419.
[2]	ZHOU M, HAN Y, YAO Y, et al. Fabrication of Ti₃C₂T_x/In₂O₃ nanocomposites for enhanced ammonia sensing at room temperature[J]. Ceramics International, 2022, 48(5):6600-6607.
[3]	DONG J, GAO Z, ZHANG Y, et al. A selective and sensitive optical sensor for dissolved ammonia detection via agglomeration of fluorescent Ag nanoclusters and temperature gradient headspace single drop microextrac-tion[J]. Biosens Bioelectron, 2017, 91: 155-161.
[4]	杜晓燕, 程五一, 闫瑞青, 等. 我国涉氨制冷企业氨泄漏事故规律性研究[J]. 消防科学与技术, 2017, 36(6):857-860.
	DU Xiaoyan, CHENG Wuyi, YAN Ruiqing, et al. Research on regularity of ammonia leakage accidents in ammonia-related refrigeration enterprises in China[J]. Fire Science and Technology, 2017, 36(6):857-860.
[5]	许佳欣, 陈程, 邱诗波, 等. 氨气传感器研究现状及智能化应用[J]. 包装学报, 2022, 14(2):57-66.
	XU Jiaxin, CHEN Cheng, QIU Shibo, et al. Research status and intelligent application of ammonia sensor[J]. Packaging Journal, 2022, 14(2): 57-66.
[6]	VEERALINGAM S, SAHATIYA P, BADHULIKA S. Low cost, flexible and disposable SnSe₂ based photoresponsive ammonia sensor for detection of ammonia in urine samples[J]. Sensors and Actuators B: Chemical, 2019.DOI:10.1016/j.snb.2019.126725.
[7]	祁福平, 党红娟. 化工企业氨气含量检测方法简评[J]. 中氮肥, 2022(5):69-72.
	QI Fuping, DANG Hongjuan. Review on detection methods of ammonia content in chemical enterp-rises[J]. M-sized Nitrogenous Fertilizer Progress, 2022(5):69-72.
[8]	谭由之. 植物染料茜素的清洁分散染色及数码印花应用[D]. 上海: 东华大学, 2022:4-6.
	TAN Youzhi. Application of vegetable dye alizarin in clean disperse dyeing and digital printing[D]. Shanghai: Donghua University, 2022:4-6.
[9]	ARRIETA M P, SAMPER M D, ALDAS M, et al. On the use of PLA-PHB blends for sustainable food packaging applications[J]. Materials, 2017.DOI:10.3390/ma10091008.
[10]	CHEN Y, GEEVER L M, KILLION J A, et al. Review of multifarious applications of poly (lactic acid)[J]. Polymer-Plastics Technology and Engineering, 2016, 55(10): 1057-1075.
[11]	YANG L, ZHANG J, WU J, et al. Influence of collagen hydrolysate components on fabrication of collagen/PVA composite fiber[J]. Textile Research Journal, 2020, 90(9/10):1141-1148.
[12]	ZHANG J, ZOU X, ZHAI X, et al. Preparation of an intelligent pH film based on biodegradable polymers and roselle anthocyanins for monitoring pork freshness[J]. Food Chemistry, 2019, 272: 306-312. doi: S0308-8146(18)31442-0 pmid: 30309548
[13]	DENG L, KANG X, LIU Y, et al. Effects of surfactants on the formation of gelatin nanofibres for controlled release of curcumin[J]. Food Chemistry, 2017, 231:70-77. doi: S0308-8146(17)30391-6 pmid: 28450025
[14]	AN N, AN Y, HU Z, et al. Graphene hydrogels non-covalently functionalized with alizarin: an ideal electrode material for symmetric supercapacitors[J]. Journal of Materials Chemistry A, 2015, 3(44): 22239-22246.
[15]	张全彩. RuO₂、MnO₂和茜素/ZIF-8衍生多孔碳复合材料的制备及其超电容性能研究[D]. 兰州: 西北师范大学, 2018:70-73.
	ZHANG Quancai. Preparation of porous carbon composites derived from RuO₂, MnO₂ and alizarin/ZIF-8 and their supercapacitive properties[D]. Lanzhou: Northwest Normal University, 2018:70-73.
[16]	严晨峰. 纤维素纳米球增强聚乳酸纳米复合材料的构筑及性能研究[D]. 杭州: 浙江理工大学, 2016:50-51.
	YAN Chenfeng. Construction and properties of polylactic acid nanocomposites reinforced by cellulose nanos-pheres[D]. Hangzhou: Zhejiang University of Science and Technology, 2016:50-51.
[17]	KONG Y, YUAN J, WANG Z, et al. Study on the preparation and properties of aligned carbon nanotubes/polylactide composite fibers[J]. Polymer Composites, 2012, 33(9): 1613-1619.
[18]	徐金龙. 胶原纤维可食用膜的机械性能改善策略及相关机制[D]. 无锡: 江南大学, 2021:30-31.
	XU Jinlong. Strategies and mechanisms for improving mechanical properties of edible collagen fiber mem-brane[D]. Wuxi: Jiangnan University, 2021:30-31.
[19]	李美琛. 茜素表面改性二氧化钛材料的制备及可见光下光催化还原六价铬的研究[D]. 天津: 天津大学, 2020:18-19.
	LI Meichen. Preparation of alizarin surface modified titanium dioxide and photocatalytic reduction of hexavalent chromium under visible light[D]. Tianjing: Tianjin University, 2020:18-19.
[20]	周歆如, 范梦晶, 岳欣琰, 等. 导电微纳纤维复合纱的制备及其气敏特性[J]. 纺织学报, 2024, 45(2):52-58.
	ZHOU Xinru, FAN Mengjing, YUE Xinyan, et al. Preparation and gas-sensitive properties of conductive micro-nano fiber composite yarn[J]. Journal of Textile Research, 2019, 45(2):52-58.
[21]	倪安琪. 变色响应聚丙烯腈纳米纤维膜的性能研究[D]. 上海: 东华大学, 2017:31-38.
	NI Anqi. Study on properties of color-changing response polyacrylonitrile nanofiber films[D]. Shanghai: Donghua University, 2017:31-38.
[22]	李秋莹, 于昕睿, 刘铮, 等. 姜黄素/茜素pH敏感蛋白纤维膜的制备及对金枪鱼鲜度的指示作用[J]. 中国食品学报, 2022, 22(10): 260-269.
	LI Qiuying, YU Xinrui, LIU Zheng, et al. Preparation of curcumin/alizarin pH sensitive protein fiber membrane and its indicator effect on tuna freshness[J]. Journal of Chinese Institute of Food Science and Technology, 2022, 22(10): 260-269.

Metrics

Viewed

Full text

Abstract

Cited

Shared

Discussed

浓度/ (mol·L^-1)	L	a	b	H/(°)	ΔE
0	82.1	-2.0	17.0	51.0	0
0.004	81.2	2.4	14.6	38.7	5.09
0.008	77.4	2.6	11.7	35.1	8.45
0.040	76.4	11.0	7.0	8.0	17.36
0.080	76.8	14	-1.4	338.5	24.95
0.400	53.5	9.9	-3.9	323.8	37.37
0.800	52.4	10.0	-5.0	317.0	38.86
1.000	45.9	13.2	-16.0	274.0	51.29